Preparation of drying oils from clay polymers



1951 I M. ADAMS ETAL 2,569,595

PREPARATION OF DRYING OILS FROM CLAY POLYMERS Filed Nov. 8, 1947 5 2 Sheets-Sheet i FLASH VESSEL VAPOR/2E1? M jETTLER z .4dsorbenf 26-- R 28 a/ v I 25/ n I3 27 g ABSORPTION 5:2 VESSEL Sludge I 35 30 FILTER 3e 34 i l 3.3 8 n2 l4ds o ibenf Vacuum 64 sm/PPER /FRACT/0NA70R Drying Oi/ Inve'nfors: Leon M. Adams SO/venf Presfon L. Brandi f0 Recycle Robgrf Lee Dr Dry/n9 'Franc/s ZWadsworf/g g Res/ n 9'! M Pafenf Aqem Oct. 2, 1951 L. M. ADAMS ET AL PREPARATION OF DRYING OILS FROM CLAY POLYMERS 2 Sheets-Sheet 2 Filed- Nov. 8, 1947 3 QMRE zotovfim QuwQnimbm 6 Shaun;

Patented Oct. 2, 1951 UNITED STATE S PATENT OFFICE PREPARATION OF DRYING OILS FROM CLAY POLYMERS Application November 8, 1947, Serial No. 784,814

1 Claim.

This invention relates to polymeric materials, commonly called clay polymers, prepared by contacting cracked petroleum distillates at elevated temperatures in the vapor phase with active solid catalysts, and more particularly to a method for preparing drying oils having improved color from such polymers;

Our invention broadly comprises contacting the said polymers or fractions thereof with a selective catalyst of a type more fully described below, whereby the color bodies in said polymers are selectively converted into an immiscible sludge; and the treated polymer is subsequently further purified by contacting it in the liquid phase with an adsorbent solid. A valuable drying oil of greatly improved color is produced by these operations.

The primary object of our invention is to prepare synthetic hydrocarbon drying oils of good color from clay polymer, a material which is at present of limited utility because of its dark color and heterogeneous composition. Another object of our invention is to devise continuous means for separating color bodies from clay polymer.

A further object of our invention is to lower the quantity of adsorbent material required for the decolorization of clay polymer. A subsidiary object of our invention is to prepare new and improved surface-coating compositions comprising clay polymer drying oils. Other objects and advantages of our invention over the prior art will be apparent from the description and examples.

In the cracking of petroleum hydrocarbons, various gum-forming materials are produced, and must be removed in order to give a product of satisfactory stability. This may be done in a variety of ways, one of the most satisfactory of which is the Gray process (USP 1,340,889, May 25, 1920). In this process, cracked hydrocarbons are passed in the vapor phase through a bed of an active solid, such as fullers earth, at an elevated temperature, for example, above about 400 F. Under these conditions, the gum and color bodies are polymerized and a highly unsaturated polymer is produced on the clay. In a typical clay-treating installation, cracked gasoline vapors are passed through a tower containing a false bottom to support the clay charge. Such a tower having a 12-foot inside diameter and a height of 19.5 feet may contain 25 tons of 30-60 mesh clay, suitably a 50:50 mixture of Floridin clay and fullers earth. The tower may be operated according to a cyclic procedure, in which it is taken off stream periodically and the polymer is washed from the clay with a suitable solvent, such as gasoline, kerosene, light naphthas, aliphatic ethers, aromatic hydrocarbons, and the like. temperature and pressure within the clay tower are adjusted so that a partial condensation of Preferably, however, the

heavier components of the gasoline vapors takes place therein. Under these conditions, the polymer tends to flow downward out ofthe clay, and the condensed hydrocarbons act as solvents to assist in the removal of the polymer from the clay. This technique makes continuous operacontain primarily aluminum silicates.

tion of the tower feasible, and moreover it prolongs the activity of the clay at a high level. Under the most suitable conditions, the polymeric product is recovered as a 20 percent concentrate in the condensed hydrocarbons. The polymer may subsequently be isolated by stripping off the solvent, preferably under vacuum, with or without the use of steam or an inert Among the numerous catalysts suitable for producing clay polymer may be mentioned bone black, charcoal, activated carbon, bauxite, silica gel, magnesium silicate, kieselguhr, infusorial earth, diatomaceous earth, and various clays, such as fullers earth and bentonite, which As specific examples of such clays may be mentioned Florida earths, known by various names such as Floridin and Florex, and Attapulgus clay. The latter may advantageously be prepared as described in U. S. Patent 2,363,876.

The polymers resulting from the Gray process in general have low volatility, high viscosity, and good drying properties, the latter resulting from their high iodine numbers, generally above about 150. Unfortunately, however,. the polymers are very dark in color, and for this reason, despite their good drying properties, they have not been utilized to any substantial extent as components of surface-coating materials.

Numerous attempts to improve the color of clay polymers have been made during the twentyseven years that have elapsed since Gray first prepared them, but little success has been achieved. It has been observed, for example, that clay-treating the polymer in the liquid phase will give a product of light-red color. However, the life of the clay in this process is extremely low, of the order of l to 2 barrels (42 gallons per barrel) of polymer per ton of clay, and for this reason the process is not economically feasible.

We have now discovered that under properly chosen conditions certain catalysts are capable of selectively degrading and sludging the greater proportion of the colorbodies in clay polymers, without aliecting the desirable drying constituents thereof to any objectionable extent. This is highly unexpected, in view of the prior art, which teaches the polymerization and removal of diolefinic (drying) constituents from petroleum fractions by treatment with acidic materials, such as sulfuric acid; and particularly in view of Osterstrom USP 2,067,334, which teaches the conversion of cracked-gasoline polymers into lubricating oils by treatment with sulfuric acid, probably through intermolecular hydrogen transfer, as disclosed by Ipatiefi and Pines (J. Org. Chem, 1, 464 (1936) The latter mechanism has alsobeen applied, for example by Thomas in USP 2,240,081, 5 to convert olefinic polymers into much more highly unsaturated materials. We have-now observed that acidic catalysts injgeneraLlashereinafter defined, attack first thecolor bodiesin clay polymer, which appear ordinarilylto constitute up to around percent by weight of the .total polymer, and we have discovered'that'the color bodies may be removed preferentially, leaving a'drying oil of good color and drying properties, if the polymer is contacted :with anlacidic'catalyst under conditions suchthat the-reduction of the iodine number of the polymenisnot greater than around 30 percent of the'original-value, andpreferably under conditionssuchithat-the iodine number is reduced between about5 and '20-percent below its original value. Onthebasis of this discovery, we have devised an improved andhighly advantageous process for decolorizing'clay polymers and for preparing superior drying oils therefrom. The process is carried out broadly as follows:

The clay polymerora fraction thereof may be dissolved in a'substantially unreactive solvent, if necessary, to reduce .its viscosity to a suitable level. The polymer or polymer fraction, or solution thereof is then contacted with the selective polymerization catalyst, whereby the color bodies are converted into asludge, which is'then separated. The purified'polymer solution is subsequently contacted with'an active clay or other adsorbent solid, 'foriexample'a material of the type used in the Grayprocess'to remove any remaining dissolved and/or suspended polymeric residues; and aftertthe solution has been separated from the clay, the solvent is-stripped ofi, leaving a purified polymer of amber to light-red color suitable for use in surface-coating compositions.

In a typical application of the Gray process, cracked gasoline vapors are passed through a bed of 30 to 60 mesh Attapulgus or Floridin clay, comprising aluminum silicates, at a temperature of 425-450 F., a pressure of 200-300 pounds per square inch, gage, and a space velocity around 5 barrels per ton per hour. Under these conditions, polymerization of color and gum-forming components of the gasoline takes place and a highly unsaturated polymer is produced. The crude clay polymer emerging from the reaction unit is in a diluted form containing 80 to 85 percent of gasoline and kerosene boiling range material, which is stripped out, for example, with steam to give socalled reduced clay polymers, the properties of which vary, depending on the extent to which the low-boiling constituents are removed. The following are theproperties of two typical reduced clay polymers:

1 Saybolt Universal Seconds (ASTM. D-68-38). 2 D155-39'1".

3 Wijs, 0.5 hr., 200% excess.

4 Menzie's method.

Drying oils of somewhat improved color may be separated from clay polymers bymeans of fractional distillation. For example, when polymer B (described above) is fractionated at 5-10 mm. .Hg in abatch still, a drying oil of appreciably lighter color may be obtained by separately collecting the 10-50% fraction withdrawn overhead, based on the quantity of polymer charged to the still. Alternatively and preferably, the clay polymer maybe subjected to a flash distillation, either under vacuum or around atmospheric pressure, whereby the material is heated rapidly to a high temperature, suitably 500 to 1200 F., for a very short period of time, optionally with the addition of an inert gas as a stripping agent, and the drying-oil constituents are vaporized andseparated from the heavier ends without the losses that ordinarily occur in the slower batch-type distillation of unsaturated compounds. By this means, we have succeeded in separating from reduced clay polymer an overhead fraction comprising up to around percent of the original material, and of a dark green color, rather than the original opaque black. We have observed, however, that the distillatesobtained by anyof these methods retain an objectionable amount of color and odor, and tend to darken on aging; and by means of our improved process we have-now succeeded in effecting a stable and greatly superior decolorization of clay polymers and clay polymer distillates.

In carrying out our'process, the clay polymer or a drying-oil fraction thereof ispreferably first dissolved in a solvent that-is-substantiallyunreactive under the processing conditions subsequently employed. Saturated aliphatic and naphthenic hydrocarbons and their halogenated derivatives in general, and-mixtures thereof, are suitable. For example, we may use pentanes, hexanes, heptanes, octanes, nonanes, decanes, and the like; or cyclopentane, methylcyclopentane, cyclohexane, and thelike; or chloroform, carbon tetrachloride, propyl bromide, and other unreactive halogenated solvents; and by operating under suitable conditionsof pressure, we may use lower-boiling members of the groups designated above, such as propane, butane, cyclopropane, dichlorotetrafiuoroethane, and the like. We have observed that ordinarily aboutonefourth to four volumes of solvent per volume of clay polymer are ample to reducethe viscosity to a suitable level, and we-prefer to usebetween about one and two volumes per volume. Higher proportions of solvent maybe used, for example, as much as 10:1 ormore; however, at the higher proportions, the expenseof recovering the solvent is increased Without any material compensating advantage in carrying out the process.

The clay polymer solution is then contacted with a catalyst capable of polymerizing the colored constituents thereof without degrading an excessive proportion of-the desired drying-oil components. For this ipurpose, polymerization catalysts of the acid type are suitable, suchas boron fiuoride,,sulfuric acid, aluminum chloride, hydrogen fluoride, mixtures of 'hydrogen'fiuoride with boron fluoride, *sulfonic acids, phosphoric acids, stannic chloride,'spent isomerization catalysts comprising complexes of aluminum chloride and hydrocarbons, and the like. AlliOf these materials are either strong mineral acids, or give such acids on hydrolysis. We ordinarily use'between about 0.5 and 20 percent of the catalyst, based on'the weight of claypolymer, and we prefer to use .between about 5 and 15 percent.

The primary action of: the 'definedclassof catae.

lysts. is .to convert the color 1 bodieslin ithe relay polymer into a sludge, but they' tendsechfidarily to attack the drying" components of the' clay polymer if their actionis'unnecessarily prolonged. For this reason, the -temperature a'nd 'the time of contact between the catalyst and polymer'solution-should be adjusted sethat any :reduction in iodinenumb'er that may occur is limitedto an amount not greater than around 30 percent of the original value, in-or'der to effect ai -maximum degree of color improvement 'without -serious im- 'pairn'lent of thedrying propertiesot the resulting 'oil. Ordinarily, we choose to operate'at-such temperatures and contact l times that thedecolorizatio'n operation can becomplet'ed without lowering the iodinenumber 'of the oil'more than about 5130 20 percent below itsoriginal-value, and preferably not more "than percent. --The optimum temperature during the polymerization reaction var ies inversely as-a-function otthe contact time for a given catalyst, and -ranges -ordinarily between about 40 and +300 =-With boron 'fiuoride', for examplepweprefer to operate in the lower part of- 'thisrange, suitably between about -40 and +100 -F. wi-th-- sulfuric acid in the middle part, --suitably between about 30 and 200 F.; and with phosphoric acids, in the-upper part, suitably between about-100 and 300 The contact'time betweenthe catalyst-and the polymer solution varies according to the-specific catalyst, the temperatureemployed, the type-ofmix ing equipment, and the desired degree ofcolor improvement. -Ingeneral, however, wehave found that 0.5-to 10 minutesof contacting in continuous orifice-mixers is sufficient, whereas in less efficiently agitated batch-type equipment the time of treating maybe considerably longer, for example up to ten hours or more.

I The pressure within the reaction vessel is not a critical reaction variable. However the pressure should preferably be kept at such a level as will maintain a sufficientquantity of solvent in the liquid phase to give a solution hav ingthe desired properties.

Ihe acidic polymerization ca-talyst converts the color bodies intoa-sludge, which settles out and may be withdrawn when thereaction mixture-is allowed to stand,- or which may be separated by other convenient means, such as centrifugation. The polymer solution remaining is then treated in the liquid phase with anactive adsorbent solid, such as thematerials suitable for use in theproduction of clay polymers by the Gray process, the residual sludge and-a portion of the residual color being removed thereby. In carrying out this treatment,-the polymer solution may, for example, be percolated through a column packed with granulated adsorbent, or the solution'may beslurried with the adsorbent in finely divided form, and subsequently filtered or centrifuged. The conditions employed -in this treatment are not'oritical. Temperatures within the range of about 30-'-to 150 F. are entirely satisfactory, andspace velocities in the percolation method up 'to about 50'barrels of polymer per ton of clay per-hour areoperative.

Ordinarily, the clay treatment, as described above, will completely remove all-entrained or dissolved acidic-materials from-the polymer solution. However, alkaline materials, such" as sodium carbonate or the like, may be incorporated with the adsorbent to assist in such removal; 'or

the polymer sclutionmay becontacted with such alkaline materials or aqueous solutions thereof, either before or after the adsorbent treatmentl 'Finally, the-solvent is' str iriped out of the treated-polymer solution-in a conventional-atmospheric or vacuum still, with or without the use of steam or an inert gas as a stripping agent. Aproduct of superior color is thereby isolated.

in carrying out "our invention, we may choose to e'm'ploy fractional distillation of the polymer at one or more stages of the process. For example, we may use a'clay polymer charging stock in the form of a liquidhaving a viscosity (prior tothe addition of solvent) of SGGAOOSayb'olt universal seconds at 100 F.; or we may prefer to strip out lower-boiling components from the polymer to give a charging stock'having a viscity of 300-500 seconds at 21051 or higher; or we may "choose tovacuum fractionate the polymer'to isolate a distillate fraction having an improved color and a higher iodine number; or we maychoose to flash-distill the crude clay polymer to isolate a fraction of improved color in substantiallygreater yield, as described more fully above. The last two alternatives, in particular, incombination with the'process of our'invention, permit the production of drying oils of light .color and excellent drying properties. At the end of our process, after the clay treatment and the separation of the solvent, we may choose to distill the treated polymer under vacuum as a rina-1 purification step, giving a product of lighter color.

In the combination process outlined above,'we have observed that one ton'of adsorbent: material consistently'produces around 12 to 15 ormore :ba'rrels (42 gallons per barrel) of refined. drying oil having an ASTM color of 4 or less in 2 percent hexane solution, prior to vacuum "distilla-ti'o'n. The adsorbent inaterial may afterwards be regenerated by washing it with an eluant comprising a lower aliphatic alcohol and/or a lower aliphatic ketone, mixed with a light aromatic or naphthenic hydrocarbon. For

'this purpose, a solution of methanol in benzene is preferred. The exhausted adsorbent material is thereby washed comparatively free from adsorbed polymers, and'is subsequently dried with an'inert gas or with superheated steam. It is then ready for reuse, with substantially the same activity as it possessed'initially. The wash liquid may be evaporated in a suitable still to recover the solvents used, and the polymeric residueih the still may then be recovered for use as a binder for carbon electrodes, cores, woodgsand, cork, and asbestos articles, and the like.

'In a preferred form of our invention, we employ sulfuric acidas the selective polymerization catalyst, suitably aqueous sulfuricacid having a concentration above '7 percent, or fuming sulfuric-acid containing up to 20 percent or more of ireesulfur-trioxide. Ordinarily, however, we choose to employ aqueous sulfuric acid having a concentration between about and pere'e'nt,'and*weprefer to contact the clay polymer solution-with the sulfuric acid for a period betweenabout 5 and 20 minutes at a temperature between about 30 and 200 F. The ratio of catalyst to polymer is preferably around 20 pounds of acid per' barrel of clay polymer distillate, and arounueo pounds per barrel of reduced clay polymer. In the subsequent treatment with'acfive-adsorbent solid, we have processed up to 100 barrels of acid-treated'reduced clay polymer 'pertonof solid, and upto 200 barrels of acidtreated'clay polymer distillate per ton of solid, beforexregeneration of the solid was'necessary. -By means' of this process, we have converted clay .polymehuistillatesin yields around 90 percent-to 7 drying oils which, without dilution, have ASTM colors below 5, and which set to touch in one to three hours and tack-free in five to ten hours after addition of conventional driers (0.3% Pb and 0.06% Mn, in the form of the naphthenates).

Figure 1 illustrates an embodiment of our invention employing flash distillation of the crude clay polymer solution, followed by treatment of the distillate with a strong inorganic acid.

Reduced clay polymer, similar to polymer B hereinbefore described, flows through line I into pump I2 and is transferred through line I3 into flash vaporizer I4. Around 90 percent of the crude polymer solution is vaporized therein, and emerges through line I5 into separator I6, where the resinous, non-vaporized material is separated and withdrawn through line H. The vapors pass through line I8 into cooler I9, from which the condensate flows through line 20 into reaction vessel 2|, of which two or more may be provided and used in succession, in order to permit continuous operation of the distillation equipment.

In reaction vessel 2|, an equal volume of an inert solvent, such as naphtha, is added through line 22, and percent by weight of 98 percent sulfuric acid, based on the weight of polymer, is introduced through line 23. The mixture is then stirred thoroughly by agitator 24 for a total average residence time of approximately 25 to 30 minutes at '70 to 120 F.

From reaction vessel 2|, the treated material is withdrawn through line 25 into settling tank 26, where the sludge is allowed to separate. The sludge layer is withdrawn from settling tank 26 through line 21, and may be accumulated for subsequent recovery of valuable chemicals contained therein.

The treated polymer solution from settler 26 flows through line 28 into adsorption vessel 29, of which two or more may be provided and used alternately. Therein, the solution is agitated by stirrer 30 and contacted with an adsorbent solid, such as fullers earth, introduced through port 3|. The resulting slurry emerges from the bottom of vessel 29 through line 32 and is forced by pump 33 through line 34 into filter 35, where the spent adsorbent is separated. The filter cake is withdrawn, revivified, and recycled; and the filtrate flows through line 36, heater 31, and line 38 into stripper column 39 at an intermediate point.

In column 39, the solvent is stripped out of the polymer solution by means of reboiler 40 and by means of steam introduced through line 4|. Solvent and water vapors emerge overhead through line 42 into cooler 43, from which the condensate flows through line 44 into separator 45. The solvent layer in separator 45 is withdrawn through line 46 and is split into two streams, one of which is refluxed to stripper 39 through valve 41, and the other is withdrawn through valve 48 and recycled through line 49, suitably to reaction vessel 2|, and preferably after being dried.

The bottom stream from stripper 39 is a purified drying oil, and may be withdrawn through valve 50 and cooler 5|. Alternatively, the bottom stream may be transferred, for further purification, through valve 52, pump 53, and heater 54 to an intermediate zone of fractionator 55, equipped with reboiler 56. Therein, the material is subjected to fractional distillation under a vacuum below about 25 mm. Hg. A drying-resin fraction is withdrawn from the bottom of fractionator 55 through line 51, heat exchanger '56,

andfline 59.- The major portion of the charge stream emerges overhead as a vapor through line 60 into cooler BI, and the resulting condensate flows through line 62 into separator 63, which is connected through line 54 to a vacuum source. A portion of the condensate is refluxed to fractionator 55 through valve 65, and the remainder is withdrawn through valve 66 and line 61 as the primary drying-oil product.

In another highly advantageous embodiment of our invention, the clay polymer is contacted countercurrently with a gasiform acidic polymerization catalyst, such as boron fluoride, preferably under conditions of temperature, pressure, contact time, and catalyst-to-polymer ratio that the ensuing reduction in iodine number of the polymer is not greater than about 10 percent. Such a process is illustrated in Figure 2, wherein the apparatus comprises fractionating towers to separate a drying-oil distillate fraction from the crude clay polymer, a continuous reactor for contacting the distillate fraction with the gasiform acidic polymerization catalyst, a semi-continuous tower for subsequently clay-treating the distillate fraction, and a continuous stripper column.

Crude clay polymer solution from the Gray towers is fed through line I I I, heater i I2, and line I I3 to an intermediate point of fractionator column II l, equipped with reboiler Il5. condenser H6, and separator III. Substantially all of the naphtha boiling up to about 600 F. is stripped out of the solution entering column H4, and is liquefied in condenser H5, from which it flows into separator II? and is split into two streams. One naphtha stream is refluxed through valve IIB to column H4, and the other is taken ofi through valve H9 and line I20, and is recycled, for example, to the clay-extraction stage of the process in which the clay polymer is made.

The bottoms from column II4, a polymer having a viscosity of 200-1000 SS U at 210 F., are transferred by pump I2I through heater I22 into vacuum still I23, equipped with reboiler I24, condenser I25, separator I26, and a vacuum-producing means applied to separator I26 through line I27. A portion of the charging stock, for example around 15-50 percent, is withdrawn at the bottom through heat exchanger I28 and line I29. This material is a highly colored drying resin having a softening point of l50-300 F., as determined by the ring-and-ball test. The major portion of the charging stock emerges overhead through condenser I25 and separator I26, and is split into two streams, one of which is refluxed to the column through valve I30, and the other is taken oil through valve |3| and transferred by pump I32 through heat exchanger I33 into the top of reaction tower I34. En route to heat exchanger I33, the polymer is diluted with a solvent, such as hexane, isobutane, or propane, supplied via pump I35 and valve I36, ordinarily in the ratio of between one and two volumes of solvent per volume of polymer, and the temperature of the mixture is adjusted to the desired level in heat exchanger I33.

The mixture of clay polymer and solvent entering the upper portion of tower I34 flows downward countercurrent to a rising vapor stream of solvent and an acidic catalyst, such as boron fluoride. contact between the two streams being promoted by a suitable packing Within the column. Any of these vapors which are not absorbed' by the descending fresh feed, mixture are condensed by cooler I31 and returned to the top oithe column through reflux drum I38. The

boron -fluoride e selectively pol-ymerizes .the color bodies-fin the.- .clay--.-P91yrner.- during, the passage of. the: mixture downward :through 1 the. column. At the- --.;bottom of.- the., column; 1 heat. is .supplied: by means of' a 'coil- I 3.9;; and solvent mayvbe supplied through valve 5! 40, vaporized in-heater I41! andintroduced into the lower P811L1Of113h6pl10W61 to, strip boronv fluoride from the bottoms. The stripped boron fluoride passes upward through the column to be reabsorbed by fresh polymer. Make-up-boron fluoride is supplied to the-col umn through line= I 4Z-to compensate for losses from the system; The treated polymer solution passesfrom. the "bottom of. the tower through cooler. l 43 into settler I 44,- from which. a sludge layer is. withdrawn. through .line. I45.

Thetreated solutionfrom settler M4 may .be. caustic-washedto :remove traces of acid catalyst (apparatus not shown); and is then transferred by pump l46 into:the-top-of treatingstower I l'l, and is allowed to flow downward: through atbed of adsorbent, suitably 3.060 mesh Flores clay, a typical fullers earth. From'the bottom of the column; .the .solutiom passes, through: heater I48 intor: stripper-.-'sti1l.- :l 49 Sat: -an:; intermediata point-.1 The solvent ,is stripped out: by reboiler I 5 i and by. steam, introduced through ,line. l! into the bottom :of ,thecolumn. .5 Steam and solvent vapors emerge. overheadand, are condensed in. cooler l 52-,;:from* which. thecondensate; flows into separator I53." 'Thezwater -layer; from separator 853 is: withdrawn through; line, 'i 54;, and is discarded or recycled; as rdesiredi- The: solvent layerisdivided into two streanisnone of which is refluxed to st-ripper: I49 through valve I55; and the other is. withdrawn: through 3 valve I 56 '5 and "recycled through line l5'l:, :suitably;td-pump. l3-5,-.prefer:- ably ,after being dried.

A .dryingoil of good color emergesvfromthe bottom of stripper: l 49 through heatexchanger I58 and line I59. a

Our invention will;be more fully understood from the following specifi'c' examples:

Example I One volume of'redu'cedclay polymer having a viscosity of B65 SSU at 210"F:, aniAsTlvL'color. of. 7 /2 in 0.5% solution in hexane, and an iodine number'of 216 was diluted with 2 volumes of pen tane, andthe solution was agitated with l2percent sulfuric acid (40 pounds of acidper barrel of reduced clay-polymer). at a temperature of 85-105 F. for minutes. Theorganic layer was decanted from the sludge and filtered t hrough Florexctowa claYlife-of around 50. barrels per ton. Onremoval-ofathe pentane,.:a product'having an ASTMbolor; undilutedpof Twas recovered in aboutr'70 percent..yield..- This-'product'wasdistilled .under: a pressure-hi 1 5-2 mm. Hg until '5 l percentk'of the materialhadbeen taken offfoverhead. The: distillate .had 1 an 2 ASTMt-color' of 2;. and dried readily. Properties. of: this: material were asfollo'wsz:

Iodine number. 183' Specifidgravity, 60/60-E';-' 0.9375 Refractive index; C; s 1.5191

The-bottoms from this. distillation. were a drying resin having. an .iodinanumber. of 194,,a ring and ballsofteningpoint-of 154 R, and an "ASTM color. of 8 in;5 percent. benzene.- solution.

Example II' Total crudeclay polymerT was. flash distilled at. atmosphericpressure with steam stripping. The total-.distillate was. subsequently, .redistilled,. and

from itwas separated .a 5-.6. percent.heavy,distil.- late .fraction having v the'folloyving properties:

ASTM'color, 10 solution 8+ 5% solution (green)1 5 Iodine number 215 Water content, percent by volume 2 Sp. gr-.,' 60/60 F 0.9738

Viscosity, 100 F.', SSU 1029 Viscosity, 210 F.; SSU' 5I Boiling range:

Per cent Fi' at 10 mm. Hg.

The distillate fraction was diluted with an equalgvolume; of light naphtha and agitated for abouti5-minutes with ten pounds of 98% sulfuric acid per barrel. Virtually all of the water was removed from the distillate fraction in the resulting aoidsludger The dried distillate solution was then agitated for 30 minutes at- -105 F. with 30 poundsof-98' percent sulfuric acid'per barrel of distillate. The resulting sludge layer was removed, and the acidtreated polymer solution waspercolated through 30-60 mesh Florex to a clay life of 60-"70 'barrels per ton; The naphthaxwas subsequently stripped out. and a productdhaving the;following prop-" erties was obtained:

A reduced clay polymer having a viscosity of 365 SSU-at 210 F. was fractionated'in a batch still at 10-25'mm; Hg, and the 5-50 overhead fraction, having a dark greenish-black color (2 ASTM in 10% solution in hexane), an iodine number of 206', and a viscosity. of 203 SSU at F., was separate'd'foruse'as the charging stock in" the preparationof an improved drying oil. The 5-50% fraction was dissolved in an equal'volurne of n-pentane" and agitated for 10 minutes at. 95F. with 6%.v by weightzof 98% sul furic acid, based on the weight of. the polymer fraction. The resulting sludge layer wasallowed to settle, and Was separated. The pentane solution was then passed at the rate of 4 barrels (42 gallons per barrel) of polymer fraction per ton of clay per; hour througha column packedwith 30-60 mesh Florex clay, and'finally the treatedsolution was stripped free of pentane with a hydrocarbon gas at F., giving a purified drying oil in 91% yield; basedaonthe Weight of polymer fraction charged. The Florex. clay life was 90.l,'barrelsof. polymer fraction per .ton. The

Example IV A clay polymer distillate (50% fraction of Example III) having an iodine number of 206 and a diluted ASTM color of 2% solution in hexane) was diluted with an equal volume of pentane and treated with 20 pounds of 96% sulfuric acid per barrel for 10 minutes at95? F. The sludge layer was separated and the treated pentane solution was percolated downward through a column filled with 30-60 mesh Florex clay which had beenactivatedby heat treatment at 1250 F. for a period of 24 hours, Theeffluent from the column was collected in sixfractions in order to determine the effectof clay age pp color. After the pentane had been stripped out of the treated fractions, products having the following properties were obtained:

Clay Age, ASTM Fraction No. bbL/ton Color Example V An opaque black reduced clay polymer having a viscosity of 300-350 SSU at 210 F. viscosity was pumped into a flash distillation apparatus comprising a 4-inch iron pipe, 24 inches long, terminating in a heated 2-inch T, which served as a separation chamber. The temperature of the pipe was maintained at 700 F. by means of a tubular combustion-type furnace, and the pressure within the separator was maintained at 10 mm. Under these conditions, the vapor phase within the separator was taken off at 550 F. and condensed, and a minor proportion of resinous, non-volatile material was withdrawn from the bottom of the separator. The overhead and residual fractions had the following properties:

The overhead fraction was diluted with an equal volume of naphtha, and the diluted material was agitated for 10 minutes at 95 F. with 20 pounds of 96 percent sulfuric acid per barrel of overhead fraction. After separation of the re- Sulting acid sludge, the naphtha solution was treated with 30-60 mesh Florex clay to a clay life of 50-100 barrels of overhead fraction per ton. Subsequently, the naphtha was stripped out of the solution with gas at a temperature around 212 F., and a drying oil was obtained having an ASTM color of 4, undiluted. When the oil was combined with driers (0.3% Pb and 0.06% Mn), it set to touch in about one hour.

Example VI The same opaque black reduced clay polymer described in Example V was flash-distilled. at. a.

Viscosity, 25 C., centipoises...

furnace temperature of 810 F., a separator pressure of 100 mm. Hg, and a vapor temperature of 610 F. in the apparatus described in Example V, and an overhead fraction was separated in a yield of 85.9% of the weight of the original charge. The properties of the overhead and residual fractions were as follows:

Specific gravity, 60/60 F Refractive index, 25 C Yield, weight per cent Softening point, F

The overhead fraction, when decolorized as in Example V, had an ASTM color of 4,5, undiluted, and the decolorized material plus driers set to touch in one hour.

Example VII A group of experiments was carried out on a reduced clay polymer having an ASTM color of 7 in 0.5% hexane solution, an iodine number of 193, and a viscosity of 346 SSU at 100 F. The reduced clay polymer was diluted 1:1 with hexane, and a stream of BFz was bubbled through the solution under the conditions indicated below. Subsequently, the solution was washed with aqueous caustic solution, and was then filtered through Attapulgus clay. A substantial improvement in color was obtained, and the losses in iodine numbers were very low, averaging less than" 10% of the original value. The process condi tions and results were as follows:

Experiment No 1 2 3 4 5 BF; treatmntz Temperature, F 5 95 95 95 140 Contact time, min 180 20 60 180 60 Clay treatment:

Temperature, F 77 77 77 77 77 Contact time, min 30 30 30 30 30 Product color:

Initial emllellt 2. 0 2 5 2. 5 2. 5 2.

Final 2 3.0 4. 5 .4. 0 4.0 4. 75 Product iodine number 194 187 188 177 188 Yield, per cent 77 86 88 83 1 ASTM, 2% solution. 1 After the Attapulgus clay had treated 15 barrels of polymer per ton.

a Weight per cent of product, based on reduced clay polymer chargng stock.

' Example VIII A clay polymer having properties as hereinafter set forth was dissolved in an equal volume of hexane, and the solution was heated on a steam bath to approximately F. Four percent by weight of powdered anhydrous aluminum chloride, based on the clay polymer, was then slowly added to the warm solution with continuous stirring. Agitation was continued at 140 F. for thirty minutes, and the mixture was then allowed to cool to room temperature. From the cooled mixture was separated 14.2 percent by weight, based on the clay polymer, of a heavy, black, tarry sludge, including aluminum chloride. Sufiicient isopentane was then added to the hexane solution to give a mixture having a ratio of about two volumes of mixed isopentane and hexane per volume of clay polymer, and the solution was passed through a column of dry Florex clay at the rate of four barrels of clay polymer per ton of clay per hour. The efiluent stream from the column was collected and freed of solvent. by stripping under vacuum. The yield of 13 product was 74%, based on the weight of clay polymer charged. The properties of the charging stock and product are compared in the following table:

1 After the Florex clay had treated 15 barrels of polymer per ton. 3 7% ASTM in 0.5% solution in hexane.

The above examples are illustrations only of various forms that our invention may take, and it is to be understood that we do not wish to be limited thereby. For example, we may choose touse a multiple-step treatment of clay polymers with acidic polymerization catalysts, and subsequently with adsorbent solids. In general, it may be said that any modifications or equivalents that would ordinarily occur to one skilled in the art are to be considered as lying within the scope of our invention.

The products of our invention are clear, amber to light-red liquids having iodine numbers that are in excess of 150 and may be as high as 250 or above, average molecular weights between about 200 and 400, drying times less than that of linseed oil, and viscosities that may be varied at will over a wide range by regulating the conditions under which the products are made. The products obtained from the preferred form of our invention have ASTM colors (undiluted) of or below. These materials have proved to have considerable utility in the formulation of airdrying and baking varnishes, as modifying resins in alkyd compositions, and as cold-cut resins in linseed oil base paints.

In accordance with the foregoing specification, we claim as our invention:

A process for preparing a drying oil of superior quality from clay polymer, which comprises distilling crude clay polymer and separating therefrom a reduced clay polymer having a viscosity between about 200 and 1000 SSU at 210 F., fractionally distilling said clay polymer at an absolute pressure between about 5 and 10 mm. Hg and separating therefrom a drying oil as a distillate fraction and a drying resin as a bottoms fraction having a softening point between about 150 and 300 F. (ring and ball test), dissolving said drying-oil distillate fraction in a petroleum naphtha in a distillate-to-naphtha ratio between about 0.25:1 and 4:1, contacting the resulting solution with between about 5 and 15 percent by weight, based on said drying-oil distillate fraction, of sulfuric acid having a concentration between about and percent for a period between about 0.5 and 10 minutes at a temperature between about 30 and 200 F., thereby polymerizing color bodies originally present in said drying-oil distillate fraction while reducing the iodine number of said fraction between about 5 and 20 percent, Withdrawing an acid sludge containing the resulting polymerized color bodies, contacting the treated solution with an active clay, separating said petroleum naphtha from the resulting clay-treated solution, and recovering a drying oil having an ASTM color below about 5 therefrom.

LEON M. ADAMS.

PRESTON L. BRANDT.

ROBERT J. LEE.

FRANCIS T. WADSWORTH.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,919,722 Hyman July 25, 1933 2,090,333 Osterstrom Aug, 17, 1937 2,092,889 Mikeska Sept. 14, 1937 2,228,789 Soday Jan. 14, 1941 2,240,081 Thomas Apr. 29, 1941 2,257,078 Soday Sept. 23, 1941 FOREIGN PATENTS Number Country Date 397,699 Great Britain Aug. 31, 1933 835,014 France Dec. 9, 1938 

